Production of valuable hydrocarbons of low boiling point



Patented Feb. 16, 1932 1,844,998

UNITED ST TES PATENT OFFICE BUDOLF wIE'rznL, on LUDWIGSEAFEN-ON-THE-BHINE, Aim connan rr'nunnnnn, or OPPAU, GERMANY, nssmuons no I. G. r'nnnnnmnus'rnm anrrmrensnnnscnnrr, or FRANKFQRT-ON-THE-MAIN, GERMANY, A CORPORATION or GERMANY PRODUCTION OF VALUABLE HYDBOCAKBONS OF LOW BOILING POINT No Drawing. Application filed l iarch 21, 1928, Serial-Ho. 263,581, and in Germany March 31, 1927.

It is already known that valuable liquid uranyl nitrate is converted into the oxid by h drocarbons may be produced from distillsplitting off of oxids of nitrogen. 'The depa le carbonaceous material, such as any osition onto the metal may also be effected kind of coals, tars, mineral oils, their disin any other way, such as by evaporating a tillation, conversion and extraction products, salt solution in the presence of the fragments 65' residues, and the like, by heating, especially of metal, by electro-chemical means or also in contact with hydrogen or gases giving off by intimately mixing in a ball mill the metal hydrogen which are equivalents for the purgranules, which may be etched beforehand, pose of the present invention, to high temwith small quantities of moistened vanadium peratures, under pressure and by the use of oxidand the like. It may also s'ometimesbe catalysts. -.of advantage to render catalytic, by activa- We have now found that it is particularly tion in the above manner, the metal walls, advantageous to employ for this process catpipes, stirring or paddle devices and the like alysts which are deposited in small quansituated in the reaction zone in which caseit 15 tities on, metals or metallic alloys which do is..not necessary that additional catalysts be not meltunder the conditions of working. employed, since the walls themselvesiserveas These metals or alloys as for example alucatalysts, but additional catalysts may of minium, silver,'manganese, chromium, chrocourse be added. This last procedure withmium nickel, silicon and the like, are prefout the employment of additional catalysts erablyused in aform presenting a dense and may be of importance, when using initial coherent surface, such for example as grains, materials containing ash liable to"produce balls, chips, ribbons, wire, wool and the like. obstructions and the deposition of coke when A great variety of substances may be used passed through. a catalyst layer. These last as catalysts, the amount of which need often drawbacks may also be more or less elimibe merely fractions of one per cent of the nated by the employment of stirring mechaamount of metal or alloy used. Particularly nisms or of a high velocity of flow. A parsuitable catalysts are the oxids or compounds ticular advantage of the catalysts according furnishing the same under the conditions of to the present invention is also their hi h Working of theelements from groups 3 to 7 heat-conducting capacity which enables t 39 of the periodic system, such as uranium oxid, otherwise readily occurring local superhea Vanadium oxid, chromic acid anhydride, 'ing within the reaction zone to be more. or Y manganese oxid, molybdenum oxid, boric less completely prevented.

' I acid, and the like,'either alone or in admix- In many instances the metal or alloy not ture with one another or with other subonly acts as a carrier, but may also possess stances. -Other substances eiiective as catacatalytic properties or acquire same by realysts comprise oxids or compounds furnishson of the treatment herein described. Many ing the same of platinum, ruthenium, cobalt, metals, such as aluminium, ossess a certain gold, cadmium, and the like. A mixture of catalytic capacity, especia y after being iron oxid, copper nitrate and cadmium nietched with acids and the like. This capacity trate may be mentioned as examples of such is considerably increased by the substances compounds. The said catalyst may be preapplied to the metal and surpasses that of the pared by treating the' metals, such as comsubstance applied when the latter is used mercial granular aluminium, preferably alone or on non metallic carriers such as charafter etclnng, for example, with hydrochlocoal, pumicestone and the like. Not only the ric acid or mercuric chlorid, with, preferably proportion of substances of lowboiling point acidified, solutions of salts of catalytic eleproduced in a single passage is increased ments, as for example by moistening with thereby but also the output capacity, Inthe 7 solutions of uranyln1trate,boric acid and the manner herein described it is easy to convert like. The said compounds furnish oxids 80 per cent and more of a petroleum fraction 50 under the conditions of working. ,Thus of a boiling point above 300 centigrade by passing it only once with hydrogen over the catalyst under a pressure of the order of pressures employed in destructive h dro enation and at about 450 centigrade into enzines boiling below 200 centigrade, even when working continuously f0 weeks with the same catalyst. I

The aforesaid catalysts are very well adapted for the production of low-boiling products of the benzine type, and are also very suitable for dehydrogenating hydrocarbons, tars, mineral oils, their distillation, conversion, extraction products and the like, or for converting the same into aromatic hydrocarbons. In such cases, the working temperatures are generally higher for example 550 to 650 centrigrade than those necessary for the production of benzines.

The methods already known for converting coals, tars, mineral oils and the like into valuable hydrocarbons, may also be applied in connection with the present process, for example such as the operation in a c clic system, prepurifying the gases, puri ying the gases in circulation, separatin the reaction products by cooling and/or y adsorbent masses or by washing with suitable liquids, means for heating the reaction components and avoiding, in those parts of the apparatus coming into contact with the hot reaction components, the presence of substances which promote the deposition of carbon or the ormation of methane this being achieved, for example, by lining the apparatus with irll1{1minium,-high-grade steel alloys and the The operations may be conducted in such a way that the hydrocarbons or the like are brought into reaction in the state of vapor wherein the operation is preferably carried out with a large excess of hydrogen, or the hydrocarbons and the like may be brought into reaction, wholly or partially in a liquid condition, in the presence of the'above de-- scribed catalysts.

The reaction components may also be ad- I mitted into the reaction chamber in the form of mist or in an atomized condition, or they may be in thin la ers, or the gases may be introduced into t e substances under treatment througha porous stratum.

The reaction components may also be sub- 0 jected to repeated treatment by heat, .with or without the presence of hydrogen or gases giving off hydrogen.

The following examples will further illustrate the nature of the said invention which however is not limited thereto.

, Example 1 A mineral oil fraction boiling above 270 an aluminium-lined pressure vessel containing a catalyst consisting of fine granules of aluminium activiated with 1 to 2 per cent of uranyl nitrate with the aid of h drochloric acid. The nitrate is converted un er the 0011-. ditions of working. In this way an oil is obtained consisting to the extent of 80 per cent and over of benzines boiling up to 200 centigrade. Similar action is exerted by a catalyst prepared by activating aluminium with boric acid.

Example 2 Example 3 Elwerath oil, boiling at above 300 centigrade, and mixed with an equal amount of an ash-free middle oil, is forced, with the aid of hydrogen, through an aluminium-lined pressure vessel at 450 centigrade. In order to obtain a high velocity of flow, suitable spiral ribbons of aluminium are arranged, so that the oil takes a spiral course. The aluminium parts are previously activated with hydrochloric acid and boric acid. In a single passage, 40 per cent and more of the crude oil is converted into benzine, and further large proportions into middle oil.

If the initial material is forced through the apparatus without the aid of hydrogen, the yield obtained in a single passage is generally somewhat lower, and moreoverthe resulting product is partially unsaturated.

f a working temperature of about 600 centigrade or higher be employed, the reaction product contains 30 per cent and more of aromatic hydrocarbons.

Example 4 A'middle-oil fraction from bituminous coal tar, boiling between 200 and 350 centigrade is passed in a current of hydrogen at 450 centigrade and 200 atmospheres pressure over a-catalyst consisting of zinc wool activated by evaporating an aqueous suspension of. blue molybdenum oxid containing the zinc wool. Even in a single passage, more than 50 per' cent of the initial materials is converted into benzine, and complete conversion into benzine is effected by further treatment in circulation.

The said middleoil may also be replaced by corresponding mineraloils. such as middle Example 5 A brown-coal-tar oil boiling substantially above 250 C. is passed at a temperature of 460 C. and at a pressure of 200 atmospheres together with hydrogen over a catalyst consisting of small compact aluminium granules on which 1 per cent of metallic silicon, and

- 0.1 per centof vanadium oxid is deposited .in a fine state of division by treatment with a solution of a salt of vanadium oxide. 'If the oil is passed over the catalyst only once, an oil is obtained per cent of which boils below 250 C.

What we claim is: v

1. A process for the production of valuable hydrocarbons of low boiling point from a distillable bituminous material which comprises subjecting said material to a heat treatment at a temperature of between 450 to 650 C. and at a pressure of the order of the pressures employed in destructive hydrogenation, in the presence of a catalyst comprising small quantities of an oxid of a 'metal of groups 3 to 7 of the periodic. system deposited on ametal, which is in a dense coherent state under the conditions of working and which, under said conditions, does not cause deposition of carbon, selected from the class consisting of aluminium, chromiumnickel, silver, manganese and chromium.

2. A process for the production of valuable hydrocarbons of low boiling point from a distillable bituminous material which comprises subjecting said material to a heat treatment with hydrogen at a temperature of between 450 and 650 C. and ata pressure of the order/of the pressures employed in destructive hydrogenation, in the presence of a catalyst comprising small quantities of an oxid of a metal of groups 3 to 7 of the periddic system, deposited on a metal, which'is in a dense coherent state under the conditions of work ing and under said conditions does not cause deposition of'carbon, selected from the class consisting of aluminium, chromium-nickel, silver, manganese and chromium.

comprising small quantities'of an oxid of a metal of roups 3 to 7 of the periodic system,

deposite on a metal, which is in a dense coherent state under the conditions of working and which, under said conditions, does not cause deposition of carbon, selected from the class consisting of aluminium, chromiumnickel, silver, manganese and chromium, by

treating said metal with an acidified solution of a-salt of-a metal of the 3rd to 7th groups of the periodicsystem, which salt yields the said oxid under the conditions of working.

4. A process for the roduction of valuable hydrocarbons of lowv oiling point from a mineral oil fraction boiling above 270 C. which comprises passing said mineral oil fraction, with an excess of hydrogen, at a temperature of about 450 C. and a pressure of 200 atmospheres, over, a catalyst comprising' an oxid of uranium deposited on granules of aluminium.

5. A process for the production of valuable hydrocarbons of low boiling point from a dis-, tillable bituminous material which comprises subjectingsaid material to a heat treatment with hydrogen at a temperature between 450 and 650. C. and at a. pressure of about 200 atm spheres in the presence of a catalyst compr sing small quantities of an oxid of a metal of group 6 of the periodic system deposited on chromium-nickel which is in a' dense coherent state, under the conditions of working.

6. The process as defi ned in claim 3 wherein the conversion is effected in the presence of an excess of hydrogen.

. thereon. a

In testimony whereof we have hereunto set our hands.

' RUDOLF WIETZEL. v

CONRAD PFAUNDLER.

.. 3. A process for the production of valuable distillable bituminous material which comprises subj ecting said material to a heat treatmentwith hydrogen at a temperature "between 450 and.650 C. and a pressure of the order of pressures employed in destructive hydrogenation, in the presence of a catalyst hydrocarbons of low boiling point from a. 

